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EP2463399B1 - Composants de magnésium dotés d'une protection contre la corrosion améliorée - Google Patents

Composants de magnésium dotés d'une protection contre la corrosion améliorée Download PDF

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Publication number
EP2463399B1
EP2463399B1 EP10194110.2A EP10194110A EP2463399B1 EP 2463399 B1 EP2463399 B1 EP 2463399B1 EP 10194110 A EP10194110 A EP 10194110A EP 2463399 B1 EP2463399 B1 EP 2463399B1
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EP
European Patent Office
Prior art keywords
alloy
group
magnesium
vitreous
elements
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP10194110.2A
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German (de)
English (en)
Other versions
EP2463399A1 (fr
Inventor
Michael Störmer
Carsten Blawert
Yuanding Huang
Daniel Höche
Wolfgang Dietzel
Karl Ulrich Kainer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Helmholtz Zentrum Hereon GmbH
Original Assignee
Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
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Publication date
Application filed by Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH filed Critical Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
Priority to EP10194110.2A priority Critical patent/EP2463399B1/fr
Priority to US13/302,418 priority patent/US20120148871A1/en
Priority to JP2011268653A priority patent/JP2012122138A/ja
Publication of EP2463399A1 publication Critical patent/EP2463399A1/fr
Application granted granted Critical
Publication of EP2463399B1 publication Critical patent/EP2463399B1/fr
Not-in-force legal-status Critical Current
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12729—Group IIA metal-base component

Definitions

  • the present invention relates to magnesium components with improved corrosion protection.
  • magnesium alloys have been used for some time due to their low strength to density ratio.
  • the biggest obstacle to the use of magnesium alloys is still the lack of corrosion resistance of unprotected surfaces.
  • magnesium oxide In the absence of moisture, magnesium reacts with atmospheric oxygen to form magnesium oxide (MgO), which forms a very thin gray layer on the surface of the material.
  • MgO magnesium oxide
  • Magnesium oxide has a smaller molar volume than the underlying magnesium matrix and therefore forms a porous layer.
  • Pilling-Bedworth ratio describes the quotient of the molar volume of the layer-forming oxide and the molar volume of the base material and is 0.84 in the case of magnesium.
  • Magnesium oxide therefore, can not protect the material as well as, for example, aluminum oxide-forming alumina having a Pilling-to-Bedworth ratio of 1.38.
  • the corrosion behavior of magnesium components is not only dependent on the humidity, but also on the chemical composition of the atmosphere.
  • the different magnesium materials show as corrosion forms surface and hole-like attack.
  • the typical corrosion rate for magnesium materials is 0.5 to 50 mm / year.
  • the corrosion protection of magnesium components usually takes place by applying protective layers to the component.
  • Protective layers are usually classified into the following categories: (a) chemical conversion layers, (b) electrochemical protective layers, (c) non-metallic protective layers, and (d) physically altered surfaces.
  • HAE HAE
  • Magoxide Coat a corrosion protection for magnesium components
  • Anomag method a corrosion protection for magnesium components
  • the HAE method is considered to be fluoride anodization or galvanic anodization using alternating current.
  • HAE layers are made up of spinel elements of the elements magnesium, aluminum and manganese, ie mixed oxides of divalent and trivalent metal ions, and belong to the anodic conversion layers. The brittle layers are about halfway into the material and half outwards. HAE coatings are applied as wear protection and corrosion protection and also serve as a primer for paints.
  • the plating of magnesium is much more difficult than, for example, the deposition of metallic coatings on steel or brass.
  • the baths commonly used for these materials are unsuitable for magnesium alloys. Due to the chemical activity of magnesium in such baths, spontaneous dip deposition of loose, poorly adhering layers occurs.
  • the mode of action of the coatings based on organic paints is based primarily on the inhibition of the access of the corrosion-promoting compounds water and oxygen to the metal surface. This penetration resistance is determined by the diffusion resistance of the lacquer layer and by its adhesion to the substrate under the action of moisture, the so-called wet film adhesion.
  • Epoxy resins are said to provide the best corrosion protection for magnesium components, followed by epoxy-polyester hybrid resins and polyester resins.
  • Organically coated magnesium components have sensitivity to filiform corrosion and are more susceptible to these than aluminum components.
  • Metallic and other conductive coatings can cause contact corrosion in the event of a defect.
  • the object is achieved by a magnesium component, which is coated with a glassy binary Mg-X alloy or a glassy ternary Mg-XY alloy, wherein X is an element selected from the group consisting of the elements of the 3rd main group, the 3rd Is subgroup or rare earth elements of the Periodic Table, and Y is an element selected from the group consisting of the elements of the 3rd or 4th main group, the 3rd or 4th subgroup or rare earth elements of the Periodic Table, and wherein the atomic ratio Mg: X in the primary Mg-X alloy 75:25 to 60:40 and the atomic ratio Mg: X: Y in the ternary Mg-XY alloy is 75:25:10 to 60: 40: 5.
  • the alloys Mg-X and Mg-X-Y may also contain other elements Z, etc. However, these further elements should preferably be present only in minor amounts of ⁇ 5 at.%, More preferably ⁇ 1 at.%, More preferably ⁇ 0.5 at.%, And most preferably ⁇ 0.1 at.% In the magnesium alloy of the coating ,
  • magnesium component designates according to the invention any component which is made of magnesium metal or a magnesium alloy. These may be components for motor vehicles, aircraft, ships, machines or the like, but also medical implants such as bone implants or the like.
  • the magnesium alloy of the magnesium component may contain any amount, for example, of 1 to 100 atomic% (at.%) Of magnesium.
  • the magnesium alloy of the magnesium component preferably contains at least 50 at.%, Particularly preferably at least 70 at.% Of magnesium. It is preferable, but not necessary, that the magnesium alloy further contains at least one element selected from the group consisting of the elements of the 3rd main group, the 3rd subgroup, or rare earth elements of the periodic table.
  • the magnesium component may be made of an AZ31, AZ91, AE42, ZM21, ZK31, ZE41 alloy or any other common magnesium alloy.
  • glass refers to an amorphous alloy which is characterized by the absence of crystal structure and the material in a kind of arrangement without periodicity, ie without long distance order. similar to the atoms in a melt remains. Although the alloys are called amorphous, they always have a pronounced order of proximity, both topologically and chemically.
  • the term "3rd main group of the periodic table” includes the elements boron (B), aluminum (A1), gallium (Ga), indium (In), and thallium (T1).
  • the term “4th main group of the periodic table” includes the elements carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb).
  • the term “3rd subgroup of the periodic table” includes the elements scandium (Sc), yttrium (Y), lanthanum (La) and actinium (Ac).
  • the term “4th subgroup of the periodic table” includes the elements titanium (Ti), zirconium (Zr) and hafnium (Hf).
  • rare earth elements includes the elements of lanthanides and the elements of actinides. Under the collective name “lanthanides” , the following are the 14 elements following lanthanum, namely cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd) , Terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yt) and lutetium (Lu). These are often present as mixed metals. In the context of the present invention, the term “rare earth element” also includes mixed metals of the rare earths or lanthanides. That means, that such a mischmetal metal can be regarded as "one element" X or Y.
  • the present invention relates to magnesium components coated with a glassy binary Mg-X alloy or a vitreous ternary Mg-XY alloy, wherein X is an element selected from the group consisting of the elements of the 3rd main group, the 3rd subgroup or Rare elements of the periodic table, and Y is an element selected from the group consisting of the elements of the 3rd or 4th main group, the 3rd or 4th subgroup or rare earth elements of the Periodic Table.
  • the components are coated with a binary Mg-X alloy, more preferably X is selected from the group consisting of Al, Gd, La and a mischmetal of the group of lanthanides.
  • the components may alternatively be coated with a ternary Mg-XY alloy, more preferably X is selected from the group consisting of Al, Gd, La and a misch metal of the group of lanthanides and Y is selected from the group consisting of B, Si, Zr is selected or another element from the group consisting of Al, Gd or La.
  • the atomic ratios of the binary alloy Mg-X are 75-60 Mg: 25-40 X, and the ternary alloy Mg-XY is 75-60 Mg: 25-40 X: 10-5 Y.
  • the corrosion properties of the layers produced have particularly low corrosion rates, if the contents of the components Mg-X or Mg-XY correspond approximately to the content of the intermetallic phases, which would form according to the state diagram in the thermodynamic equilibrium.
  • the components are coated with a binary Mg-X alloy in which X is Al. Due to the possibility of galvanic corrosion, the potential of the coating should be lower than that of the substrate.
  • Y is an element selected from the group consisting of the elements of the 3rd or 4th main group, the 3rd or 4th subgroup or Rare elements of the periodic table is.
  • Y is selected from the group consisting of Zr and La. The content of Y is 5 to 10 at.%.
  • the components are coated with a binary Mg-X alloy in which X is Gd. Further optimization is achieved if another element is added to form a Mg-XY alloy, in which Y is an element selected from the group consisting of the elements of the 3rd or 4th main group, the 3rd or 4th subgroup or Rare elements of the periodic table is.
  • Y is selected from the group consisting of B, Si, Zr and Al. The content of Y is 5 to 10 at.%.
  • the components are coated with a binary Mg-X alloy in which X is La.
  • a further element is added to form a Mg-XY alloy, in which Y is an element selected from the group consisting of the elements of the 3rd or 4th main group, the 3rd or 4th subgroup or rare earth elements of the Periodic table is.
  • Y is selected from the group consisting of B, Si, Zr and Al. The content of Y is 5 to 10 at.%.
  • the coatings according to the invention can be produced by means of physical gas deposition processes, preferably by cathode ray sputtering (sputtering).
  • sputtering cathode-ray sputtering method
  • a cathode-ray sputtering method for coating substrates in which plasma generates ions, preferably noble gas ions, such as argon ions, which are accelerated in the direction of a cathode and impinge there on a material to be sputtered, namely the coating material (target), in a vacuum chamber well known.
  • a cathode-ray sputtering method for coating substrates in which plasma generates ions, preferably noble gas ions, such as argon ions, which are accelerated in the direction of a cathode and impinge there on a material to be sputtered, namely the coating material (target), in a vacuum chamber well known.
  • a magnet is mounted under the target (magnetron sputtering
  • combinations of two coating materials are used to produce a binary Mg-X alloy on the surface of the component.
  • combination in the present context means a combination of at least two separate coating materials (targets), which are atomized by different cathode beams.
  • targets which are atomized by different cathode beams.
  • a combination of magnesium as a first coating material and at least one second coating material is preferably used, wherein the second coating material (X) is an element selected from the group consisting of the elements of the 3rd main group, the 3rd subgroup or R is rare earth elements of the Periodic Table, and Y is an element selected from the group consisting of the elements of the 3rd or 4th main group, the 3rd or 4th subgroup or rare earth elements of the Periodic Table.
  • the first and second coating materials are preferably atomized by cathode rays generated by different generators.
  • a combination of magnesium as a first coating material, a second coating material (X) and a third coating material (Y) is preferably used, wherein X is as defined above and Y is an element selected from the group consisting of the elements of the 3rd or 4th Main group which is 3rd or 4th subgroup or rare earth elements of the Periodic Table.
  • Alloy targets of corresponding composition of the glassy binary or ternary or more complex alloy layer, or several alloy targets of different composition, which yield the desired layer composition only on the substrate, can equally be used for the production.
  • the samples are in the high vacuum of a system, preferably at a base pressure of less than 10 -7 mbar.
  • the required sputtering gas is preferably argon and the preferred sputtering gas pressure is 0.0001 to 1 mbar.
  • the process of the invention allows high quench rates in the range of greater than about 10 6 K / s.
  • the glassy alloys according to the invention form with grain sizes in the range of preferably ⁇ 10 nm (determined by means of transmission electron microscopy), which can not detect long-range order.
  • Such a microstructure can not be produced by conventional coating methods.
  • the preferred layer thickness of the coating is about 5 nm to 500 ⁇ m, more preferably 1 to 10 ⁇ m.
  • the magnesium components according to the invention have a low corrosion rate of less than 0.01 mm / year. Furthermore, there is a cathodic corrosion protection of the magnesium components.
  • Various magnesium-aluminum coatings with different Mg Al ratios on silicon and AZ31 alloys were prepared by sputtering two different targets, namely an Mg target and an Al target, with different energy cathode beams.
  • the coating thickness was about 3 microns
  • the vacuum was previously about 10 -7 mbar
  • the sputtering gas was argon, which was used with a gas pressure of 0.2 Pa.
  • FIG. 1 shows the corrosion rate (solid line) in ⁇ m / year and the free corrosion potential (dashed line) in mV as a function of the aluminum concentration (in% by weight) of the coating.
  • the corrosion potential of the coating is in the range of 0 to 50 wt.% Below the potential of the substrate (AZ31), which reduces the risk of galvanic corrosion.
  • Good passivation is in the range of 40-50 at.% Al.
  • the layers are also in this area very low corrosion rates with a minimum of about 5 ⁇ m / year.
  • Table 1 gives an overview of various properties of the alloys: Table 1 Mg: power / W Al: power / W Mg-coating rate / nm / s Al-coating rate / nm / s Al-Conc. / wt.% Layer thickness / ⁇ m Roughness / nm d hkl nm Grain size / nm obtained phases Free corrosion potential / mV Corrosion rate / micron / year Passive current density / mA / cm 2 Breakthrough potential / mV 160 0 0815 0 0 2.5 33 2608 29 hcp Mg -1,832 671 active resolution active resolution 130 30 0743 0085 7 2.8 1.0 2587 31 Mg (Al) -1870 399 active resolution active resolution 160 60 0387 0095 11 2.8 1.3 2578 27 Mg (Al) -1866 369 active resolution active resolution 160 80 0924 0183 13 3.1 1.1 2558 21 Mg (Al
  • FIG. 2 shows the corrosion rate in mm / year as a function of the gadolinium concentration (in At.%) of the coating.
  • the corrosion rate in the Mg-Gd system also drops significantly as the microstructure of the coating becomes nanocrystalline / amorphous.
  • FIG. 3 shows the corrosion rate in ⁇ m / year as a function of the lanthanum concentration (in At.%) of the coating.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (11)

  1. Élément de construction à base de métal magnésium ou d'un alliage de magnésium, qui est revêtu avec un alliage binaire Mg-X vitreux ou un alliage ternaire Mg-X-Y vitreux, X étant un élément choisi dans le groupe constitué par les éléments du groupe IIIA, du groupe IIIB ou des terres rares du tableau périodique des éléments, et Y étant un élément choisi dans le groupe constitué par les éléments du groupe IIIA ou IVA, ou du groupe IIIB ou IVB, les lanthanides ou les actinides du tableau périodique des éléments, et le rapport atomique Mg:X dans l'alliage binaire Mg-X valant de 75:25 à 60:40 et le rapport atomique Mg:X:Y dans l'alliage ternaire Mg-X-Y valant de 75:25:10 à 60:40:5.
  2. Élément de construction selon la revendication 1, qui est revêtu avec un alliage biriaire Mg-X vitreux, X étant choisi dans le groupe constitué par Al, Gd, La et un mischmétal du groupe des lanthanides.
  3. Élément de construction selon la revendication 1, qui est revêtu avec un alliage ternaire Mg-X-Y vitreux, X étant choisi dans le groupe constitué par Al, Gd, La et un mischmétal du groupe des lanthanides et Y étant choisi dans le groupe constitué par B, Si, Zr ou un autre élément choisi dans le groupe constitué par Al, Gd ou La.
  4. Élément de construction selon l'une quelconque des revendications précédentes, dans lequel l'épaisseur de couche du revêtement vaut de 5 nm à 500 µm.
  5. Élément de construction selon l'une quelconque des revendications précédentes, qui est produit à partir d'un alliage de magnésium qui contient plus de 70 % en atomes de magnésium.
  6. Élément de construction selon la revendication 5, dans lequel l'alliage de magnésium est un alliage AZ31.
  7. Procédé pour la production d'un revêtement avec un alliage binaire Mg-X vitreux ou un alliage ternaire Mg-X-Y vitreux sur un élément de construction à base de métal magnésium ou d'un alliage de magnésium, au moyen d'un procédé de dépôt physique en phase vapeur, X et Y étant tels que définis dans la revendication 1.
  8. Procédé selon la revendication 7, caractérisé en ce qu'on utilise comme procédé de dépôt physique en phase vapeur un procédé de pulvérisation par jet cathodique (procédé de pulvérisation cathodique).
  9. Procédé selon la revendication 8, caractérisé en ce que le procédé de pulvérisation cathodique est un procédé de pulvérisation cathodique par magnétron.
  10. Procédé selon l'une quelconque des revendications 8 et 9, caractérisé en ce qu'on effectue la production du revêtement avec un alliage binaire Mg-X vitreux ou un alliage ternaire Mg-X-Y vitreux par un procédé combinatoire avec des cibles d'éléments correspondant au nombre des composants, en réglant la puissance des générateurs respectifs de manière à réaliser la composition favorable souhaitée.
  11. Procédé selon l'une quelconque des revendications 8 et 9, caractérisé en ce qu'on effectue la production du revêtement avec un alliage binaire Mg-X vitreux ou un alliage ternaire Mg-X-Y vitreux en utilisant une ou plusieurs cibles en alliage.
EP10194110.2A 2010-12-08 2010-12-08 Composants de magnésium dotés d'une protection contre la corrosion améliorée Not-in-force EP2463399B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP10194110.2A EP2463399B1 (fr) 2010-12-08 2010-12-08 Composants de magnésium dotés d'une protection contre la corrosion améliorée
US13/302,418 US20120148871A1 (en) 2010-12-08 2011-11-22 Magnesium Components with Improved Corrosion Protection
JP2011268653A JP2012122138A (ja) 2010-12-08 2011-12-08 向上した防食性を有するマグネシウム部品

Applications Claiming Priority (1)

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EP10194110.2A EP2463399B1 (fr) 2010-12-08 2010-12-08 Composants de magnésium dotés d'une protection contre la corrosion améliorée

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EP2463399B1 true EP2463399B1 (fr) 2014-10-22

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US11491257B2 (en) 2010-07-02 2022-11-08 University Of Florida Research Foundation, Inc. Bioresorbable metal alloy and implants
DE102012021241A1 (de) 2012-10-29 2014-04-30 Airbus Operations Gmbh Zusammensetzung für die lokale Applikation von chemischen Konversionsschichten
WO2016118444A1 (fr) * 2015-01-23 2016-07-28 University Of Florida Research Foundation, Inc. Alliages atténuant et bloquant les rayonnements, procédés de fabrication de ceux-ci et articles les comprenant
JP7009472B2 (ja) * 2017-05-30 2022-01-25 三井金属鉱業株式会社 スパッタリングターゲット

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JP2713470B2 (ja) * 1989-08-31 1998-02-16 健 増本 マグネシウム基合金箔又はマグネシウム基合金細線及びその製造方法
JP2937518B2 (ja) * 1991-03-07 1999-08-23 健 増本 耐食性に優れた防食用犠牲電極用材料
JP2001207255A (ja) * 2000-01-27 2001-07-31 Akihisa Inoue マグネシウム合金及びその製造装置ならびにその製造方法
EP1826811A1 (fr) 2006-02-22 2007-08-29 Applied Materials GmbH & Co. KG Pulvérisation avec une cible refroidie
JP6031219B2 (ja) * 2007-03-15 2016-11-24 新日鐵住金株式会社 溶融Ｍｇ−Ｚｎ系合金めっき鋼材及びその製造方法

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EP2463399A1 (fr) 2012-06-13
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